CN109200969B

CN109200969B - Method for low-temperature plasma double-electric-field auxiliary treatment of carbon dioxide and/or carbon monoxide-containing gas synthetic compound

Info

Publication number: CN109200969B
Application number: CN201810717278.9A
Authority: CN
Inventors: 夏亚沈; 陈锋; 马晓迅
Original assignee: Hychar Holding Ltd
Current assignee: Hychar Holding Ltd
Priority date: 2017-07-03
Filing date: 2018-07-03
Publication date: 2021-06-01
Anticipated expiration: 2038-07-03
Also published as: CN109200970A; CN109200969A; CN109206296A; CN109200970B

Abstract

The invention provides a method for low-temperature plasma double-electric-field auxiliary treatment of a carbon dioxide and/or carbon monoxide-containing gas synthetic compound; the method comprises the steps of forming plasma double electric fields by utilizing two corona discharge electric fields with different electric polarities in a plasma auxiliary reactor, introducing reaction gas into the reactor, wherein the reactor contains the corona discharge double electric fields which comprise a first electric field and a second electric field, and the first electric field is a positive corona discharge electric field or an alternating current corona discharge electric field or other electric field sources capable of providing enough energy to oxidize and decompose reaction gas molecules into atoms, ions, free radicals and the like; the second electric field is a negative corona discharge electric field, and organic compounds such as aliphatic hydrocarbon, high-carbon ether, high-carbon alcohol, high-carbon ester, low-carbon alcohol and the like are obtained after reforming and reduction; inorganic compounds such as N can also be obtained₂、O₂、H₂SO₄、NH₃And so on.

Description

Method for low-temperature plasma double-electric-field auxiliary treatment of carbon dioxide and/or carbon monoxide-containing gas synthetic compound

Technical Field

The invention belongs to the technical field of plasma-assisted chemical reactions, and particularly relates to a method for synthesizing organic compounds and inorganic compounds by low-temperature plasma double-electric-field assisted treatment of carbon dioxide and/or carbon monoxide-containing gas.

Background

Water gas is the gas produced by the passage of water vapor through hot coke, and is primarily composed of carbon monoxide and hydrogen, and has a composition of approximately: CO 2₂Is 5% and H₂50% of CO, 40% of CO and N₂Is 5%; water and carbon dioxide can be discharged after combustion. Its combustion speed is 7.5 times that of gasoline, its antiknock property is good, according to the foreign research and patent report, its compression ratio can be up to 12.5, its heat efficiency can be raised by 20-40%, power can be raised by 15%, fuel consumption can be reduced by 30%, and the tail gas can be purified by using small quantity of platinum catalyst. Compared with alcohol and ether, the method simplifies the manufacture and reduces the equipment, and has lower cost and investment. The compression or liquefaction is similar to the hydrogen, but CO is not removed, and the station building investment is low. The investment and costs for compression (and also for alcohol ether production) or liquefaction can also be partly compensated with reduced costs and investments.

The synthesis gas is a raw material gas for chemical synthesis by using hydrogen and carbon monoxide as main components. Is obtained by converting carbonaceous minerals such as coal, petroleum, natural gas, coke oven gas, refinery gas, sludge, biomass and the like. Biomass and sludge also produce large quantities of synthesis gas upon pyrolysis or gasification, and they may also be referred to as coal gas, ammonia synthesis feed gas, methanol synthesis gas, etc., depending on the source, composition and use of the synthesis gas, distinguished from the gas components formed. At present, research on the synthesis of clean fuels, such as ethanol and methanol, using water gas and/or synthesis gas is being carried out, but there are some problems in the conversion process, for example, most of the current methanol synthesis from water gas and/or synthesis gas is gas phase chemical reaction, water gas and/or synthesis gas reacts to form methanol by the action of catalyst, some impurities are difficult to remove, most of the catalysts commonly used in the reaction process are noble metal supported catalysts, and impurities mixed in water gas and synthesis gas can easily deactivate the noble metal catalysts, thus further increasing the cost, therefore, providing a catalyst-free method for efficiently converting water gas and/or synthesis gas into clean fuels is certainly an effective energy technology process.

Flue gas is a gaseous substance which is produced by burning fossil fuels such as coal and pollutes the environment. As these materials are usually exhausted from a flue or chimney. The components of the composite material are nitrogen, carbon oxides (such as carbon dioxide and carbon monoxide), oxygen, water vapor, nitrogen oxides (such as nitrogen monoxide and nitrogen dioxide) and sulfides (such as hydrogen sulfide and sulfur dioxide), and the content of inorganic pollutants is more than 99%; the content of dust, powder slag and sulfur dioxide is less than 1 percent. At present, most of the waste gas generated by the combustion of the fossil fuel is discharged into the atmosphere through a flue or a chimney, and if a method for effectively solving the waste gas in the flue gas can be provided and reasonably utilized to be converted into clean fuel, the method is necessarily more effective energy utilization.

A plasma is an aggregate of electrons, ions, atoms, radicals, molecules, and the like, which are excited by gas molecules by energy such as heat or an electric field, and the number of positive and negative charges in the aggregate is substantially equal, and hence the plasma is called a plasma. Depending on the plasma energy state, temperature and ion density, high temperature, hot and cold plasmas can be distinguished. In cold plasma, electrons may have kinetic energy of 5eV or more, and molecules, radicals, atoms, and the like may be in a range from room temperature to several hundreds of degrees. Electrons with sufficient energy can generate inelastic collision with gas molecules to convert the gas molecules into excited particles, free radicals (or atoms), ions and other active particles, so that reactants are activated, and catalytic reactions which are difficult to perform in mechanics can be performed at a lower temperature.

Common cold plasma generation techniques include silent discharge, corona discharge, glow discharge, microwave discharge, and radio frequency discharge, among others. Wherein the silent discharge and the corona discharge can generate cold plasma at normal pressure. Corona discharge utilizes asymmetric electrode discharge to generate high-energy electrons at low temperature, while silent discharge is gas discharge with an insulating medium between electrodes, and the insulating medium can prevent spark discharge or arc discharge from generating between the electrodes.

At present, cold plasma technology has become a leading-edge hot topic in the fields of environmental governance, energy development and the like, and researches on air purification, desulfurization and denitrification, gas conversion and the like by using plasma reaction have been widely carried out, but no report has been made on the combination of the cold plasma generation technologies, particularly on a method for synthesizing organic compounds and inorganic compounds by using low-temperature plasma double-electric-field auxiliary gas phase reaction.

Disclosure of Invention

The invention aims to provide a more effective method for the low-temperature plasma double-electric-field auxiliary treatment of a synthetic compound containing carbon monoxide and/or carbon dioxide; the method of the invention utilizes two corona discharge electric fields with different electric polarities in a plasma auxiliary reactor to form a plasma double electric field, utilizes electric energy to convert gas into gas molecules, atoms, ions and/or free radicals, and then obtains organic compounds or inorganic compounds after reforming and reduction. The device for realizing the method comprises a reactor with two plasma regions with different corona discharge electric fields, wherein the corona discharge electric fields are a first electric field and a second electric field which are connected in sequence, an alternating-current corona discharge electric field or a positive corona discharge electric field is arranged in the first electric field, and a negative corona discharge electric field is arranged in the second electric field, namely, strong oxidation is firstly carried out under the action of electrons, and then strong reduction and reforming are carried out to generate a target product. Various gas molecules, such as CH, can be used in an alternating corona discharge field or a positive corona discharge field₄、CO₂、CO、O₂、H₂、H₂S、H₂O、SO₂And NO_x(e.g. including NO or NO)₂) In which oxidation or decomposition takes place to produce various active components, e.g. O₃、H^-、H、CH₃And CO, whereas in a subsequent negative corona discharge field, molecules, atoms, ions and/or radicals of the gas produced by oxidation or decomposition tend to entrain electron movements in a densely erupted population of electrons, rapidly aggregate collisions, be forcibly reduced and reformed into a more stable product which may include, for example, one or more of the following organic substances, such as aliphatic hydrocarbons (e.g. heptane, 16, 18 and 20 alkanes), higher ethers (e.g. ethylene glycol but dodecyl ether), higher alcohols (e.g. dodecanol, tetradecanol), higher esters (e.g. methyl palmitate, methyl stearate, dibutyl phthalate, diisooctyl phthalateEsters, methyl oleate, methyl linoleate, etc.), lower alcohols (e.g. CH)₃(OH),C₂H₅(OH), etc.) and CO (NH)₂)₂Inorganic compounds such as N₂、O₂、H₂SO₄、NH₃And the like.

The invention provides a plasma double electric field assisted gas phase reaction method, which comprises the following steps: introducing reaction gas into a reactor, wherein the reactor contains corona discharge double electric fields, the double electric fields comprise a first electric field and a second electric field, and the first electric field is a positive corona discharge electric field, or an alternating current corona discharge electric field, or other electric field sources capable of providing enough energy to oxidize and decompose reaction gas molecules into atoms, ions, free radicals and the like; the second electric field is a negative corona discharge electric field. Preferably, the gas passes through the first and second electric fields in sequence.

According to the invention, the reaction gas is a gas comprising carbon monoxide and/or carbon dioxide, for example a flue gas, water gas, synthesis gas and/or automobile exhaust.

Preferably, the reaction gas is flue gas and water vapor, water gas or synthesis gas optionally mixed with hydrogen.

Preferably, the positive corona discharge electric field is a high voltage positive dc corona discharge electric field, and is also preferably a high frequency high voltage positive dc corona discharge electric field.

Preferably, the negative corona discharge electric field is a high-voltage negative direct-current corona discharge electric field, and is also preferably a high-frequency high-voltage negative direct-current corona discharge electric field.

The invention adopts non-thermodynamic equilibrium plasma technology, and gas molecules are excited by electric field energy to form an aggregate consisting of electrons, ions, atoms, free radicals, molecules and the like. In the cold plasma, electrons can have kinetic energy of about 4-6eV, and electrons with sufficient energy can generate inelastic collision with gas molecules to convert the gas molecules into active particles such as excited particles, free radicals (or atoms) and ions, so as to activate reactants. Corona discharge can generate plasma under normal pressure discharge by using an asymmetric electrode, dielectric barrier discharge can generate repeated electron collision with a medium in a crack of an insulating medium under normal pressure or even higher than atmospheric pressure, current density is increased, electric field intensity is strengthened, and therefore rapid and effective chemical reaction is caused. The electrons in the plasma generated in the mode are fast in speed, the thermodynamic temperature is high (for example, 11000K), and the gas temperature is close to room temperature, so that a non-equilibrium thermodynamic system is formed, the reaction system is not limited by the law of thermodynamic equilibrium composition, and all reactants are converted into products to the maximum extent. On one hand, electrons emitted by the electrode have high enough energy to excite, dissociate and reform reactant molecules, so that the reactant molecules and ions are fully reacted in a short time and converted into products; on the other hand, the gas of the reaction is kept at low temperature or close to room temperature, so that the low-temperature gas molecules can effectively obtain the thermodynamic energy required by chemical decomposition or synthesis for rapid reaction, thereby reducing the unnecessary energy consumption of high-temperature and high-pressure processing. It should be noted that such a dual field excitation reaction system may eliminate or reduce the use of catalyst, while also making it possible to avoid the use of high temperature, high pressure process equipment. In the conventional catalytic process, one often has to heat some complex metal catalyst particles by high temperature and high pressure to activate electrons on the surface of the metal catalyst material, thereby constructing an excited micro electric field with a large specific surface area to guide and compress gas molecules around the surface of the aggregated particles for rapid decomposition and reforming. However, the double electric field plasma auxiliary excitation reaction technology of the invention can artificially lead all gas oxidation and reduction reactions to obtain electric energy without a catalyst, and achieve positive or negative electromagnetic polarization in a polar strong electromagnetic field space to rapidly gather, and rapidly carry out decomposition and reforming. The method also provides a thermodynamically most optimized choice and process opportunity for the reactant gases to be efficiently oxidized and reduced, or decomposed and reformed to reach a stable product end point without any thermodynamic equilibrium composition limitations.

The alternating corona discharge electric field or the positive corona discharge electric field and the negative corona discharge electric field of the present invention are not particularly limited, and any plasma source known in the art may be used in the present invention.

According to the present invention, the main functions of the alternating corona discharge electric field or positive corona discharge electric field are oxidation and reforming reactions to decompose gas molecules into ions and other radicals, which in effect creates an intensified gas oxidation electric field, and any gas molecules and charged particles are forced to undergo oxidation reactions under the influence of the positive ion field or alternating electric field. Then the negative ions and molecules are reduced and converted into new molecules in the negative corona discharge electric field, namely, an enhanced reduction electric field is actually constructed, so that the molecules and charged particles are in a dense free electron group, the obtained electrons are forcibly reduced and reformed, and different gas molecules and charged particles can rapidly perform reduction reaction. In fact, such corona discharge dual electric fields can reform or wrap high energy electrons onto dissociated molecular or ionic outer orbits to produce new particles with different bond energies, making them storage media for electrical energy. This corona discharge dual-field plasma assisted reaction process technology may make it possible to effectively perform a chemical process of strong oxidation or strong reduction by artificially applying the polarity of a positive or negative electric field.

It should be noted that when the first electric field is an ac corona discharge electric field, the gas may be decomposed or oxidized in the positive upper half band of the ac corona discharge electric field, and the reductive reforming will be performed in the negative lower half band. However, the polarity of such electric field is alternately changed rapidly at a high frequency. Since the alternating frequency is too high (for example, 20kHz), the time for recombining some product molecules is often longer than the decomposition time of reaction molecules, the oxidatively decomposed particles do not necessarily have time to be reduced in response to the change of the negative electric field, and even if some particles are reduced and reformed into compounds in the lower half wave band of the negative polarity, the compounds are immediately decomposed again in the next positive wave band, so that a stable product cannot be achieved, and therefore, the preparation of the stable product cannot be realized by separately arranging an alternating corona discharge electric field. Moreover, a great deal of experimental evidence also confirms that the total effect of the alternating corona discharge electric field is often similar to the oxidative decomposition effect achieved by the positive corona discharge electric field.

According to the invention, the reaction gas is introduced into the reactor, firstly through an alternating corona discharge electric field or a positive corona discharge electric field, and then through a negative corona discharge electric field to emit electrons to provide energy to the gas molecules. Electrons are provided in the area of the alternating corona discharge electric field or the positive corona discharge electric field to bombard gas molecules, so that the gas molecules are decomposed or the molecules lose electrons, and under the action of the positive corona discharge electric field (the electrons return to a positive electrode), the compounds lose oxygen atoms, and decomposed small molecules, positive ions or free radicals are formed to be oxidized.

As an example, in particular CO₂For example, in this zone mainly CO₂By electron reaction to produce CO and O₂. Corona discharge is carried out on the electrode of the negative corona discharge electric field in the negative corona discharge electric field area, a large number of negative electrons are released and adhered to the surface of the molecule, and CO and H₂The gas molecules trap these energetic electrons to form high energy electronegative gas ions, e.g. H^-，CO^-Or H^-Plasma, which will be forced to re-reduce or reform into another stable compound, such as an organic or inorganic compound, with the release of oxygen, thereby minimizing the energy of the system.

In the present invention, the reactive gas includes but is not limited to CH₄、CO₂、CO、O₂、H₂、H₂S、H₂O、SO₂And NO_x(e.g. including NO or NO)₂) In the region of an alternating corona discharge field or a positive corona discharge field, the following reactions are mainly likely to occur:

CO₂+e^-＝＝＝＝>CO+1/2O₂ ^-

CO+H₂O+e^-＝＝＝＝>CO₂+H₂ ^-

CH₄+H₂O+3e^-＝＝＝＝＞CO+3H₂ ^-

CH₄+CO₂+2e^-＝＝＝＝＞2CO+2H₂ ^-

CH₄+1/2O₂+2e^-＝＝＝＝＞CO+2H₂ ^-

H₂O+e-<＝＝＝＝>OH^-+H⁺

2SO₂+2H₂O+3O₂+2e^-＝＝＝＝>2H₂SO₄+2O₂ ^-

NO_x+x/2e^-＝＝＝＝>1/2N₂+x/2O₂ ^-

NO_x+e^-＝＝＝＝>N·+xO·+e^-

2H₂S+3O₂+e^-＝＝＝＝>2SO₂+2H₂O+e^-

in the negative corona discharge field region, the following reactions mainly occur:

H₂+2e-＝＝＝＝>2H-<＝＝＝>H₂ ^-

2N·+2O·+e^-＝＝＝＝>N₂+O₂ ^-

N₂+3H₂ ^-＝＝＝＝>2NH₃-

4NO+6H₂O+5e^-＝＝＝＝>4NH₃+5O₂ ^-

CO₂+2NH₃+e^-＝＝＝＝>CO(NH₂)₂+H₂O^-

2CO+3H₂ ^-＝＝＝＝>C₂H₅(OH)+^-+5e^-

CO+2H₂ ^-＝＝＝＝>CH₃(OH)+2e^-

(n+1)H₂ ^-+nCO＝＝＝＝>C_nH_(2n+2)+n/2O₂+2(n+1)e^-

according to the present invention, the reaction gas is reformed to obtain a mixed gas, and the contents of the components in the obtained product are slightly different according to the raw material gas and the electric field intensity, but under the conventional operating conditions, the reformed gas mixture is treated to obtain a gas-phase product and a liquid-phase product, and the treatment may be a separation treatment by a gas-liquid separator or a distiller, such as a water-cooled condensate separator.

Preferably, if steam is included in the reaction gas, the liquid-phase product is further subjected to distillation to separate water, preferably by using an atmospheric distillation tower, and the water is further heated into steam to be recycled to the reactor to continuously participate in reforming.

According to the present invention, different organic and inorganic compounds are prepared by adjusting the electric field strength of a plasma double electric field, which is adjusted by the distance between an electric field center electrode and an opposite electrode, whether an insulating medium is added, and the dielectric constant thereof.

Preferably, the device has a housing, reaction chambers are arranged in the device, wherein at least one reaction chamber has an alternating corona discharge electric field or a positive corona discharge electric field, at least another reaction chamber has a negative corona discharge electric field, an electrode or a metal rod is arranged in the center of the corona discharge electric field, and an alternating corona discharge electric field source or a positive corona discharge electric field source and a negative corona discharge electric field source supply power to the electrode or the metal rod; the electrodes or metal rods provide high energy electrons that can be adsorbed to the gas.

According to the invention, the reaction chamber is a metal cylindrical reaction chamber or a metal tubular reaction chamber; a central electrode or a central metal rod is arranged in the center of a metal cylindrical reaction chamber or a metal tubular reaction chamber, a counter electrode or a counter metal rod is arranged at the far end (such as the ground), an insulating medium cylinder is not arranged in the electric field, and a weak electric field is generated in a corona discharge double electric field;

the double electric fields are weak electric fields, and gas containing carbon monoxide and/or carbon dioxide is reformed into a gas mixture product containing ethanol and methanol under the action of the plasma double electric fields;

according to the invention, the reaction chamber is a metal cylindrical reaction chamber or a metal tubular reaction chamber; arranging a central electrode or a central metal rod in the center of the metal cylinder type reaction chamber or the metal tube type reaction chamber, arranging a counter electrode or a counter metal rod on the outer wall of the metal cylinder type reaction chamber or the metal tube type reaction chamber, optionally, placing an insulating dielectric cylinder such as glass, ceramics, silica gel, wood and bamboo in the electric field to form a Dielectric Barrier Discharge (DBD) discharge gap to form a dielectric barrier discharge field, and generating a strong electric field in the corona discharge double electric fields;

the double electric field is a strong electric field, and gas containing carbon monoxide and/or carbon dioxide is reformed into organic compounds containing aliphatic hydrocarbon, high-carbon ether, high-carbon alcohol, high-carbon ester and the like or N under the action of the plasma double electric field₂、O₂、H₂SO₄、NH₃And the like.

According to the invention, after the mixed gas obtained by reforming the reaction gas is condensed and separated, wherein the gas phase mainly comprises carbon monoxide and/or carbon dioxide which are not available for reaction, and the main product in the liquid phase is mainly determined by the strength of a plasma electric field in a device for realizing the reaction; for example, when the reaction electric field is a strong electric field, it generates organic compounds such as aliphatic hydrocarbons, higher ethers, higher alcohols, higher esters, etc.; when the reaction electric field is a weak electric field, it mainly generates lower alcohols such as ethanol and methanol.

A plurality of the double electric field reactors are connected in series, and the gas-phase product of the former reactor is introduced into the latter reactor, so that the carbon source in the gas phase is further converted into an organic compound or an inorganic compound. In particular, a plurality of weak electric field reactors may be connected in series to further reform the gaseous components of the unconverted carbon monoxide and/or carbon dioxide and convert the carbon dioxide components to CO and H₂Further synthesize more lower alcohols such as ethanol.

The invention also provides the application of the method in preparing organic compounds or inorganic compounds.

Preferably, the device converts a gas containing carbon monoxide and/or carbon dioxide into an organic or inorganic compound.

The apparatus used is not particularly limited in the present invention, and in particular, as described above, the alternating corona discharge electric field or the positive corona discharge electric field and the negative corona discharge electric field may be any known apparatus in the art.

Preferably, the dual electric field device of the present invention is as follows: the device has corona discharge double electric fields, wherein the first electric field is an alternating current corona discharge electric field or a positive corona discharge electric field or other electric field sources which can provide enough energy to oxidize and decompose various gas molecules into atoms, ions, free radicals and the like, and the second electric field is a negative corona discharge electric field.

According to the invention, it is preferred that the first electric field is a positive corona discharge electric field.

According to the invention, preferably the positive corona discharge electric field is a high voltage positive direct current corona discharge electric field, such as a high frequency high voltage positive direct current corona discharge electric field.

According to the present invention, preferably said negative corona discharge electric field is a high voltage negative dc corona discharge electric field, such as a high frequency high voltage negative dc corona discharge electric field.

According to the present invention, the positional relationship between the first electric field and the second electric field is not particularly limited, and the first electric field may be located, for example, in an upper portion of the device or in a lower portion of the device; accordingly, the second electric field is located in a lower portion of the device, or in an upper portion of the device.

According to the invention, the gas can firstly pass through the first electric field, and then the product mixture obtained after the treatment by the first electric field enters the second electric field, or firstly pass through the second electric field, and then the product mixture obtained after the treatment by the second electric field enters the first electric field, and different gas processing purposes can be realized by different electric field setting sequences.

Preferably, the sequence of the gas passing through the corona discharge double electric fields is set as follows: firstly, the alternating current corona discharge electric field or the positive corona discharge electric field is entered, and then the negative corona discharge electric field, namely an alternating current-negative corona double electric field or a positive-negative corona double electric field is entered; or the gas is sequentially set to be as follows through the double electric fields: firstly enters a negative corona discharge electric field and then enters an alternating corona discharge electric field or a positive corona discharge electric field, namely a negative-alternating corona double electric field or a negative-positive corona double electric field.

Preferably, the device is provided with a shell, a reaction chamber is arranged in the device, a corona discharge double electric field is arranged in the reaction chamber, one electric field is an alternating corona discharge electric field or a positive corona discharge electric field, the other electric field is a negative corona discharge electric field, an electrode or a metal rod is arranged in the center of the corona discharge double electric field, and an alternating corona discharge electric field source or a positive corona discharge electric field source and a negative corona discharge electric field source supply power to the electrode or the metal rod; the electrodes or metal rods provide high energy electrons that can be adsorbed to the gas.

Preferably, the housing of the device is grounded.

Preferably, the device is provided with a gas inlet and a gas outlet, wherein the gas inlet is used for filling gas into the corona discharge double-electric-field reaction chamber, and the gas outlet is used for removing gas products.

Preferably, a condensation separator is arranged outside the reactor and communicated with the gas outlet, and the condensation separator is provided with a liquid outlet and a gas outlet.

Preferably, gas filters are disposed between the first and second electric fields, near the gas inlet and gas outlet. The gas filter is preferably a material having a physical and/or chemical adsorption function, such as a fibrous filter mesh, a packed bed of particles (such as activated carbon or molecular sieve), a packed bed of tourmaline particles (generally having a function of decomposing moisture in the air to generate a trace amount of hydrogen to reduce ozone).

As described above, the product of the dual electric field device of the present invention is determined by the electric field intensity, and when it is a strong electric field, it generates organic compounds such as aliphatic hydrocarbons, higher ethers, higher alcohols, higher esters, and inorganic compounds; when the reaction electric field is a weak electric field, it mainly generates lower alcohols such as ethanol and methanol. The strength of the plasma electric field is related to the applied voltage, the distance between the positive and negative electrodes, whether a dielectric medium is added, and the like, as is well known in the art. Therefore, one skilled in the art can adjust the above characteristics of the dual electric field device to obtain a strong electric field or a weak electric field to produce different organic or inorganic substances according to actual production requirements. The following are several specific examples of the strong electric field or the weak electric field according to the present invention.

As an example, the reaction chamber is a metal cylinder type reaction chamber or a metal tube type reaction chamber; a central electrode or a central metal rod is arranged at the center of the metal cylindrical reaction chamber or the metal tubular reaction chamber, an opposite electrode or an opposite metal rod is arranged on the outer wall of the metal cylindrical reaction chamber or the metal tubular reaction chamber, and a strong electric field is generated in a corona discharge double electric field; the positive electric field in the strong electric field can be used for oxidizing and decomposing gas molecules, and the negative electric field is mainly used for reducing and reforming to synthesize organic compounds, such as aliphatic hydrocarbon, high-carbon ether, high-carbon alcohol, high-carbon ester and the like, and can also be used for synthesizing inorganic compounds;

preferably, the central electrode or the central metal rod is connected with the negative electrode of the negative corona discharge electric field source, and the opposite electrode or the opposite metal rod is connected with the positive electrode of the negative corona discharge electric field source to form a strong negative electric field; and/or the central electrode or the central metal rod is connected with the positive electrode of the alternating current corona discharge electric field source or the positive corona discharge electric field source, and the opposite electrode or the opposite metal rod is connected with the negative electrode of the alternating current corona discharge electric field source or the positive corona discharge electric field source to form a strong positive electric field.

As an example, the reaction chamber is a metal cylinder type reaction chamber or a metal tube type reaction chamber; a central electrode or a central metal rod is arranged in the center of a metal cylindrical reaction chamber or a metal tubular reaction chamber, a counter electrode or a counter metal rod is arranged at the far end (such as the ground), and a weak electric field is generated in a corona discharge double electric field; the weak electric field is used to form organic compounds such as lower alcohols methanol or ethanol.

Preferably, the central electrode or the central metal rod is connected with the negative electrode of the negative corona discharge electric field source, and the opposite electrode or the opposite metal rod is connected with the ground to form a weak negative electric field; and/or the central electrode or the central metal rod is connected with the positive electrode of an alternating current corona discharge electric field source or a positive corona discharge electric field source, and the opposite electrode or the opposite metal rod is connected with the ground to form a weak positive electric field.

Preferably, the alternating corona discharge electric field or the positive corona discharge electric field and the negative corona discharge electric field are arranged up and down, the electric field into which the gas is firstly introduced is arranged at the lower part, namely the lower part of the device, the electric field into which the gas is subsequently introduced is arranged at the upper part, namely the upper part of the device, the gas inlet is arranged at the bottom of the device, and the gas outlet is arranged at the top of the device.

Preferably, an insulating medium thin-layer cylinder can be further placed between the central electrode or the central metal rod and the outer wall of the metal cylindrical reaction chamber or the metal tubular reaction chamber, the insulating medium cylinder can be made of materials with different dielectric constants, such as glass, ceramics, silica gel, wood, bamboo and the like, a gas crack channel is formed between the insulating medium thin-layer cylinder and the outer wall, namely a Dielectric Barrier (DBD) discharge structure is formed, and the electric field intensity of the metal cylindrical reaction chamber and the metal tubular reaction chamber is enhanced, so that the reaction process is strengthened. The principle is that an insulating medium is inserted into a discharge space to form a medium crack, blocking restriction is generated on electrons, the electrons generated by discharge repeatedly collide with the medium, the current density is increased by the discharge, the electric field intensity is enhanced, and accordingly severe chemical reaction is caused. The dielectric barrier discharge can be at a very high gas pressure (10)⁴-10⁶Pa) and frequency (50Hz-1 Mz).

Preferably, the diameters and the number of the metal cylindrical reaction chambers and the metal tubular reaction chambers are not particularly limited, and may be conventionally selected by those skilled in the art, for example, as shown in fig. 1, 1 metal cylindrical reaction chamber may be used, or more than 2 metal cylinders or metal tubes may be used to form a reaction tube array; when a plurality of metal cylinders or metal pipes are selected, the metal cylinders or the metal pipes have no influence on each other, so that the arrangement mode is not particularly limited, and the metal cylinders or the metal pipes can be reasonably selected according to the size of the device.

Preferably, the number of the metal cylindrical reaction chambers or the metal tubular reaction chambers in each electric field section is one or more, and a plurality of the metal cylindrical reaction chambers or the metal tubular reaction chambers are arranged together to form a cylinder or tubular group.

Preferably, the diameter of the metal cylinder reaction chamber or the metal tube reaction chamber is not particularly limited, and for example, a metal cylinder or a metal tube having a large diameter (for example, 70mm or more) may be used, or a metal cylinder or a metal tube having a large number and a small diameter (for example, 30 to 70mm) may be used; the specific selection also needs to be reasonably selected according to the electric field intensity and the gas quantity to be processed;

it is also well known to those skilled in the art that the relative size of the diameter of the metal cylinder or tube also affects the electric field strength within the reaction chamber. For example, when a central electrode or a central metal rod is disposed at the center of a metal cylindrical reaction chamber or a metal tubular reaction chamber, and an opposite electrode or an opposite metal rod is disposed on the outer wall of the metal cylindrical reaction chamber or the metal tubular reaction chamber, if a metal cylinder or a metal tube with a larger size is selected, the distance between the positive electrode and the negative electrode of the electric field is larger than that of the metal cylinder or the metal tube with a smaller size, and the electric field intensity inside the metal cylinder or the metal tube with the smaller size is smaller than that formed inside the metal cylinder or the metal tube with the; likewise, the electric field strength can also be adjusted by the introduction of a medium; the insulating medium layer is added into the electric field with weaker electric field intensity originally, so that the electric field intensity of the electric field can be greatly enhanced; therefore, the electric field intensity in the first electric field and the second electric field can be reasonably designed by those skilled in the art according to the factors such as the diameter of the metal cylindrical reaction chamber or the metal tubular reaction chamber, the dielectric constant of the insulating medium substance, the voltage of the external power supply and the like, and then the preparation of different organic compounds and inorganic compounds can be realized.

Preferably, a baffle is arranged between the upper bottom surface and the lower bottom surface of the corona discharge double electric field and the device shell for blocking and closing, so that the gas passage is unique.

Preferably, the number of said central electrodes is one or more, said electrodes may for example be saw tooth tip electrodes to generate an alternating corona discharge field or a positive corona discharge field around the electrodes and a double field of negative corona discharge fields around the electrodes.

In some embodiments, the electrode is a wire or needle shaped element having a sharp point at the tip of the electrode. The cusp provides a very high charge region around it. The electrodes in the reaction chamber generate electrons by forming an alternating corona discharge electric field or a positive corona discharge electric field or a negative corona discharge electric field at the electrode tips. The electrons are generated in the corona at the tip of the electrode. These electrons are adsorbed on the chemical gas molecules around the tip of the electrode, and in the dual electric field device of the present invention, about 4-6eV of energy is required for the migration of electrons from the surface of the corona electrode for the metal material suitable as an electrode in the device of the corona discharge electric field. The electrodes may be of the following materials: gold, steel, nickel, copper, silver, iron, tungsten, carbon, or platinum. The electrode material is not particularly limited in the present invention, and any material capable of forming corona to generate electrons may be used.

The electrodes may also be coated with metal catalysts, among which are useful noble metal catalysts: gold, nickel, rhodium, cobalt, phosphorus, cesium and platinum. Any noble metal catalyst capable of generating electrons may be used.

Preferably, the shape of the electrodes may be needle-shaped or linear. If the electrode has a sharp point, the potential difference of the gas adjacent to the sharp point will be much higher than other locations around the electrode. Eventually, the resulting high potential electronegative ions will transfer charge to adjacent low potential regions, which will recombine to form gas molecules.

The principle and arrangement of the metal rod are preferably the same as for the electrode.

Preferably the metal rod is selected from a fine metal rod.

Other sources that can provide sufficient energy for electrons to be transferred to a gas can also be used in the present invention. Electronegative gas ions may also be generated by other non-thermal or thermal plasma techniques or by negative ion sources, including high frequency methods such as radio frequency plasma, microwave plasma inductively coupled plasma, and the like, such as Electron Beam (EB). Any method that produces electronegative gas ions of sufficient energy and reactivity with the gas can be used in the present invention.

The operating conditions of the process and apparatus for plasma-assisted gas phase reactions of the present invention are as follows: the operation can be carried out at normal pressure and room temperature, the reaction gas is fed into the device in gaseous form, the treatment gas amount can be arbitrarily selected, the power input is increased along with the increase of the number of a plurality of discharge metal cylinders or metal pipes in the device and the treatment gas amount, the voltage can be 3000-300000 volts, preferably 10000-200000 volts, such as 15000 volts, and the frequency is 15-35 kHz, preferably 20kHz, 25kHz or 35 kHz. It should be understood that these conditions are a range of possible preferred operating conditions of the present invention, but that the key to achieving the method and objects of the present invention is the use of the plasma corona discharge double field itself, which can be determined by routine experimentation, and are not limited to the specific description above.

In some examples, when the product gas mixture generated by the double electric field device contains large amount of water vapor besides ethanol, the product gas mixture is introduced into a condensation separator for gas-liquid separation, residual carbon monoxide and/or carbon dioxide and other uncondensable gases are recycled to participate in reforming, and the liquid containing ethanol and water is separated from the gas and sent to the next working section, such as an atmospheric rectification tower for rectification, so as to form high-concentration ethanol.

In one embodiment, the ethanol aqueous solution reformed by the apparatus of the present invention may be rectified to achieve an ethanol concentration of more than 83%, preferably up to 95%.

In addition, other advantages brought by the method and the device of the invention are obvious to those skilled in the art based on the disclosure of the invention. Other aspects and advantages of the invention are described in detail in the following detailed description of the invention.

In conclusion, the method for synthesizing the compound by the low-temperature plasma double-electric-field auxiliary gas-phase reaction has the following advantages:

1) the low-temperature plasma double-electric-field auxiliary reforming process adopts a non-thermodynamic equilibrium plasma technology, gas molecules firstly pass through an alternating-current corona field or a positive plasma corona electric field and then enter negative corona discharge to collide with discharge electrons to obtain high energy to carry out decomposition and reforming reaction to obtain ethanol, and the process can be carried out at normal pressure and low temperature, so that the high cost and the technical difficulty caused by high temperature and high pressure in the prior art are avoided.

2) The plasma double-electric-field auxiliary method can reform flue gas by using water vapor to obtain a gas product, the gas product is separated by a condenser, the gas can be continuously and circularly treated after being discharged, and the water solution product is sent into an alcohol rectifying tower as a liquid phase to be dehydrated to obtain fuel ethanol, so that the product post-treatment process is mature and effective, and the production cost is low.

3) The plasma double electric field auxiliary method can directly utilize the water gas and/or synthesis gas generated by coal gas to reform, namely, carbon dioxide in the water gas and/or the synthesis gas is converted into carbon monoxide, and all the carbon monoxide and hydrogen are reformed into ethanol. Therefore, the invention can directly utilize coal to prepare ethanol fuel, and avoid complex and tortuous process and catalyst.

4) Gases including carbon monoxide and/or carbon dioxide are present in large amounts, but the recycling rate is not high, thus causing economic loss and environmental pollution. The invention adopts low-temperature plasma double electric fields to assist in recycling gas containing carbon monoxide and/or carbon dioxide, reforms the carbon monoxide and/or the carbon dioxide into high-carbon organic compounds by using a strong electric field, and reforms the high-carbon organic compounds into low-carbon alcohol by using a weak electric field, so that the gas containing the carbon monoxide and/or the carbon dioxide is changed into valuable, and clean combustion energy can be produced. In particular, in china and even global industrial combustion systems, flue gases are present in large quantities without any effective recycling, thus causing serious economic losses and environmental pollution. The invention adopts plasma high-frequency high-voltage double electric fields to recycle flue gas and uses H₂O reforms carbon oxides into ethanol, nitrogen oxides into inert gas, sulfides into sulfuric acid droplets which are easy to separate or remove, avoiding gaseous SO₂Discharge into the atmosphere, facilitating cleaning of the atmosphere or avoidance of sulfur-based fine particles or PM_2.5Formed in the atmosphere. In a word, the invention changes the flue gas into valuable, purifies the air and produces clean combustion at the same time.

5) The reforming process of the present invention, carbon monoxide and/or carbon dioxide, such as flue gas and water vapor, can be reformed primarily to ethanol in a weak electric field. And a plurality of reactors can be connected in series, and water vapor is recycled and separated, so that carbon monoxide and/or carbon dioxide are continuously converted into ethanol products, and finally, the carbon monoxide and/or carbon dioxide are completely converted into ethanol products. By the process of the invention, especially by using the series connection of the multi-stage reactors, the conversion rate of carbon monoxide and/or carbon dioxide in flue gas or water gas or synthesis gas can reach more than 50%, preferably more than 60%, more preferably 70%, even more preferably more than 80%. Particularly, the first electric field is an alternating current corona electric field or a high-voltage high-frequency positive direct current corona electric field, the second electric field is a double-electric-field reaction of a high-voltage high-frequency negative direct current corona electric field, the conversion rate of carbon monoxide and/or carbon dioxide converted into ethanol can reach more than 90%, and if a plurality of reaction devices are connected in series, the conversion rate of carbon monoxide and/or carbon dioxide can reach more than 95%.

Drawings

FIG. 1 is a schematic view showing a specific configuration of an apparatus for plasma-assisted gas phase reaction according to the present invention.

FIG. 2 is a flow diagram showing a specific process of the gas mixer and separator connected to the reactor according to the present invention.

FIG. 3 is a flow diagram of a specific process of the gas mixer and separator connected to the reactor of the present invention.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made to the invention after reading the contents of the present invention, and equivalents may fall within the scope of the invention defined by the present invention.

"gas" as described in the present specification and claims refers to those gases in which atoms or molecules are capable of capturing additional electrons to form electronegative ions. Other technical and scientific terms used herein have the same general meaning as is known in the art.

The following describes examples of the present invention using electrodes to provide alternating corona discharge electric fields or positive corona discharge electric fields or negative corona discharge electric fields. It is to be understood that the invention is not so limited and that electrodes capable of generating a plasma discharge in a sufficiently high energy state to generate electrons may also be used in the present invention.

Fig. 1 shows a schematic view of a specific configuration of the apparatus for plasma-assisted gas phase reaction according to the present invention. In the corona discharge double electric field, the reaction gas preferentially passes through a high-frequency alternating-current corona discharge electric field or a high-frequency high-voltage positive direct-current corona discharge electric field and is converted into positive ions and free radicals in the electric field, and then passes through a high-frequency high-voltage negative direct-current corona discharge electric field, is reduced in the electric field and is converted into a product.

In one embodiment of the apparatus of the invention, the reactor has a corona discharge double electric field, i.e. a high frequency alternating corona discharge electric field or a high frequency high voltage positive direct current corona discharge electric field and a high frequency high voltage negative direct current corona discharge electric field. The voltage is a high voltage, for example 15000 volts. The high frequency is a high frequency voltage, for example 25 kHz. In the reactor, there is an electrode or anode in the high frequency ac corona discharge electric field or high frequency high voltage positive dc corona discharge electric field region and an electrode or cathode in the high frequency high voltage negative dc corona discharge electric field region. The two corona discharge fields may provide a sufficiently high energy, for example 5eV, to convert the gas molecules. The device 117 has an outer shell that may be made of carbon steel, stainless steel, or other suitable material.

Two cylindrical or

tubular reaction chambers

111 and 118 are provided in the device 117 formed by the housing, wherein the material of the cylindrical or tubular reaction chambers can be made of stainless steel, carbon steel or copper and other metals. The center of each cylindrical or tubular reaction chamber is provided with a

central electrode

112 and 116, which is a needle or sawtooth rod electrode with a pointed tip. The center electrode 116 in the first electric field applies a high-frequency positive direct-current voltage (or AC) to form a high-frequency high-voltage positive direct-current corona discharge electric field (or a high-frequency alternating-current corona discharge electric field). A high frequency negative dc voltage is applied to the center electrode 112 in the second electric field to form a high frequency high voltage negative dc corona discharge electric field. The voltage (intensity) should be chosen to satisfy the following conditions: the gas delivered to the apparatus can be highly ionized in the metal cylinder or metal tube

type reaction chambers

111 and 118.

An insulating dielectric cylinder 122 is disposed between the center electrode and the cylinder body to form a Dielectric Barrier Discharge (DBD) in the electric field, and provide a narrow collision reaction zone to enhance the decomposition of all molecules into radicals or ions, thereby forming product molecules and enhancing the electric field strength of the plasma-assisted reaction process. The insulating medium cylinder 122 is made of, for example, glass, ceramic, silicone, or a teflon sheet.

The electrode material of the

center electrodes

112 and 116 may be nickel, iron, steel, tungsten, nickel, copper, silver, iron, carbon, or platinum, or any other material that can be used for the electrodes and that generates a corona around the electrodes to generate electrons. The electrodes may also be coated with metal catalysts, among which are useful noble metal catalysts: gold, nickel, rhodium, cobalt, phosphorus, cesium and platinum. Any noble metal catalyst capable of generating electrons may be used.

In operation, when the center electrode 116 is energized by an ac corona discharge field or a positive corona discharge field source, a positive corona is formed at the tip of the center electrode 116 and a positive corona field discharge is formed, the energetic electrons hit the gas molecules, and if an insulating dielectric cylinder 122 is added, a DBD may be formed to enhance the electric field strength to enhance the oxidation reaction. When the center electrode 112 is energized by the negative corona discharge field source, a negative corona is formed at the tip of the center electrode 112 and a negative corona field discharge is formed, mainly for the reduction and reforming reactions.

High voltage electricity is sent to the

center electrodes

112 and 116 through the cable

electrode distribution plates

115 and 123 for discharging. Two cylindrical or

tubular reaction chambers

111 and 118 are connected to opposing

electrodes

120 and 121, respectively. The housing 117 of the device is connected to the ground.

Gas filters 127, 128 and 129 are provided at the opening 113 at the bottom of the apparatus, the opening 110 at the top of the apparatus, and the communication of the dual electric fields, respectively, and can be used for gas filters having functions required for adsorbing harmful chemicals and particles.

The gas mixture is fed into the corona discharge double electric field inside the apparatus through an opening 113 in the bottom of the apparatus. Some gas molecules may receive discharged electrons in a high frequency ac corona discharge field or a high frequency high voltage positive dc corona discharge field for oxidation and reformation. In the high-frequency high-voltage negative DC corona discharge electric field, the gas oxide or ion can be reduced and converted again. As product is removed through opening 110 at the top of the apparatus and passes through condenser 133 to effect gas-liquid separation, liquid can be removed through port 125 and gas can be removed through port 124.

In a preferred embodiment of the present application, the central electrode 116 is connected to the positive pole of a positive corona discharge field source, and the counter electrode 120, opposite the central electrode 116, is arranged on the outer wall of the reaction chamber and connected to the negative pole of the positive corona discharge field source, in which a strong positive field is formed. The central electrode 112 is connected to the negative pole of the negative corona discharge electric field source, and the counter electrode 121 opposite to the central electrode 112 is disposed on the outer wall of the reaction chamber and connected to the positive pole of the negative corona discharge electric field source, forming a strong negative electric field in the negative corona discharge electric field.

In a preferred embodiment of the present application, the central electrode 116 is connected to the positive electrode of a positive corona discharge field source, and the counter electrode 120 is grounded, creating a weak positive field within the positive corona discharge field. The central electrode 112 is connected to the negative pole of a negative corona discharge field source, and the counter electrode 121 is grounded, forming a weak negative field within the negative corona discharge field.

By using the above device, gases from different sources can be reformed, and organic compounds such as aliphatic hydrocarbon, high carbon ether, high carbon alcohol, high carbon ester and the like and N can be formed under strong electric field according to the strength of the electric field₂、O₂、H₂SO₄、NH₃And the like inorganic compounds; for example, lower alcohols are formed under a weak electric field.

As further illustrated by the following examples, the reaction gas is introduced into the reactor, and high energy electrons are provided by an alternating corona discharge electric field or a positive corona discharge electric field, and a negative corona discharge electric field. In the reaction area of the alternating corona discharge electric field or the positive corona discharge electric field, high-energy electrons or high-energy positive charges are provided to decompose gas molecules, the gas molecules can be activated to carry out decomposition and oxidation reactions, the gas molecules capture the high-energy electrons to form high-energy electronegative gas ions, and the negative ions are reformed and reduced to form ethanol and methanol, so that the energy of the system is minimized.

Preferably, the reaction chamber is a metal cylinder type reaction chamber or a metal tube type reaction chamber; a central electrode or a central metal rod is arranged in the center of a metal cylindrical reaction chamber or a metal tubular reaction chamber, an opposite electrode or an opposite metal rod is arranged at the far end (such as the ground), an insulating medium cylinder is not arranged in the electric field, and a weak electric field is generated in the corona discharge double electric field.

Wherein, as an example, water gas and/or synthesis gas is introduced into the weak electric field reaction chamber, and CO is mainly in the alternating current corona discharge electric field or the positive corona discharge electric field₂By electron reaction to produce CO and O₂ ^-. In the negative corona discharge electric field area, the high negative potential electric negative electrode performs corona discharge to release electrons, CO and H₂The gas molecules trap these energetic electrons to form high energy electronegative gas ions, e.g. H^-，CO^-Or H^-And plasma negative ions are generated, the negative ions are reformed and reduced to form ethanol and methanol, and oxygen or negative oxygen ions are released at the same time, so that the energy of the system is minimized. The specific reaction is as follows: water gas and/or CO as the main constituent in synthesis gas₂The following main reactions occur in the alternating corona discharge electric field or positive corona discharge electric field region:

2CO₂+e^-＝＝＝＝>2CO+O₂ ^-

in the negative corona discharge electric field area, the main chemical reaction process is that carbon monoxide and charged hydrogen negative ions spontaneously synthesize ethanol and methanol, and negative oxygen ions are released:

H₂+2e^-＝＝＝＝>2H^-<＝＝＝>H₂+2e^-

4CO+6H₂ ^-＝＝＝＝>2C₂H₅OH+O₂ ^-+5e^-

CO+2H₂ ^-＝＝＝＝>CH₃(OH)+2e^-

in the present invention, the water gas and/or syngas is reformed to obtain a mixed gas product containing product ethanol and a small amount of methanol (up to a 6:1 molar ratio). The reformed mixed gas containing ethanol and methanol is condensed by a condenser and then separated into a gas phase and a liquid phase, wherein the gas phase mainly contains carbon monoxide which is not available for reaction, the liquid phase mainly contains ethanol and a small amount of methanol. Combination of Chinese herbsOne mole of ethanol molecule requires 2 moles of CO and 3 moles of hydrogen, i.e. at least H is required₂and/CO is 1.5. For conventional coal-to-water gas, the molar ratio of hydrogen to carbon is generally 1, when all H is equal to 1₂Or hydrogen atoms are reformed into ethanol molecules, and about 33% of the CO is left unreacted. If the residual CO is fully utilized, a certain proportion of hydrogen can be supplemented in the water gas, so that more ethanol is generated. However, for synthesis gas obtained by reforming natural gas, the hydrogen to carbon molar ratio is generally 4, and the hydrogen to carbon molar ratio requirement for ethanol synthesis can be ensured. The hydrogen-carbon ratio is supplemented and adjusted appropriately for the syngas and hydrogen-carbon compositions produced by the different processes, according to the traditions of the syngas manufacturing industry, in order to construct a syngas with a hydrogen-carbon molar ratio H/C of 1.5, for more efficient plasma-assisted ethanol synthesis.

A continuous process flow diagram for water gas and/or syngas reforming is shown in fig. 2, with water gas and/or syngas entering gas mixer 130 and gas entering reactor 117 through valve 132. After reforming, the ethanol-containing mixed gas enters a water-cooled condensation separator 133 for gas-liquid separation, the gas which contains residual carbon oxides and cannot be condensed is recycled to the inlet 113 of the reactor 117 or enters a gas mixer 130 for further reforming, and the ethanol-containing liquid is separated from the gas and collected.

After a period of time during which the water gas and/or syngas is passed into the reactor, additional hydrogen is added through inlet 113 to further convert the unreacted water gas and/or syngas gas.

Wherein, as an example, flue gas and water vapor are introduced into the weak electric field reaction chamber, and electrons and H are mainly in the alternating current corona discharge electric field or the positive corona discharge electric field area₂OH formation by O collision^-And H atom or H₂，CO₂By electron reaction to produce CO and O₂ ^-Sulfide SO₂Adding electrons to H₂O and oxygen O₂The reaction produces sulfuric acid liquid, nitrogen oxide NO_xWhen electrons are decomposed, N and O radicals may be formed. Negative corona discharge electric field in reaction zone of negative corona discharge electric fieldThe electrode of (2) is subjected to corona discharge to release electrons, CO and H₂The gas molecules trap these energetic electrons to form high energy electronegative gas ions, e.g. H^-，CO^-Or H^-Plasma negative ions which reduce reforming to form ethanol and methanol and simultaneously, N and O radicals are reduced to form N₂And O₂ ^-Thereby achieving the minimum system energy. The specific reactions in an alternating corona discharge electric field or a positive corona discharge electric field are as follows: carbon oxides, nitrogen oxides and sulfur compounds within the flue gas may react with added water vapor, as well as oxygen included within the flue gas, in an alternating corona discharge electric field or a positive corona discharge electric field, but are not limited to, primarily as follows:

CO+H₂O+e-＝＝＝＝>CO₂+H₂ ^-

2CO₂+e^-＝＝＝＝>2CO+O₂ ^-

2SO₂+2H₂O+3O₂+2e-＝＝＝＝>2H₂SO₄+2O₂ ^-

NO_x+e-＝＝＝＝>N·+xO·+e-

2H₂S+3O₂+e-＝＝＝＝>2SO₂+2H₂O+e^-

in a negative corona discharge electric field, the main chemical reaction process is that carbon monoxide and charged hydrogen negative ions spontaneously synthesize ethanol and methanol, and negative oxygen ions are released; reduction of N and O radicals to form N₂And O₂ ^-：

H₂+2e-＝＝＝＝>2H-<＝＝＝>H₂ ^- (11)

4CO+6H₂ ^-＝＝>2C₂H₅(OH)+O₂ ^-+5e^- (18)

CO+2H₂ ^-＝＝>CH₃(OH)+2e- (19)

2N·+2O·+e-＝＝＝＝>N₂+O₂ ^- (13)

In the present invention, flue gas and steam may be introduced into the reactor in a volume ratio, typically determined by the concentration of carbon oxides in the flue gas, with an excess of steam generally being beneficial to drive the chemical process forward. Carbon oxides and steam H₂The molar ratio of O is advantageously chosen to be 1: 2.

More importantly, a plurality of double electric field reactors can be connected in series to further reform and treat the unconverted carbon oxide gas components, namely CO is added as much as possible₂Are all converted into CO and O₂ ^-Then reforming with hydrogen decomposed from water vapor or directly adding hydrogen to synthesize more ethanol. By doing so, almost all of the carbon oxides can be converted step by step into ethanol liquid fuel. At normal temperature, the liquid ethanol can be easily transported to a wide area and used as fuel or chemical raw materials for automobiles and transportation.

The continuous process flow diagram of flue gas and steam reforming is also shown in fig. 3, compared with fig. 2, the meaning of the devices represented by the same reference numerals in fig. 2 and fig. 3 is also the same, the difference is mainly that the liquid product obtained by preparation is further rectified because the reaction feed gas contains water vapor, and the water obtained after rectification is returned to the system again, so that the water is recycled; specifically, flue gas and water vapor enter gas mixer 130 and the gas enters reactor 117 through valve 132. After reforming, the mixed gas containing ethanol enters a water cooling condensation separator 133 for gas-liquid separation, the gas containing residual carbon oxides and incapable of condensing is circulated back to the gas mixer 130 for further reforming, the liquid containing ethanol and water is separated from the gas and is conveyed to the next section, and the tower bottom of the atmospheric pressure rectifying tower 134 is rectified. And the volatile components at the top of the rectifying tower enter a collector 136 to obtain 80-95% high-concentration ethanol solution or industrial alcohol. The high boiling point water separated from the bottom of the rectification column can be sent to the steam heater 135 to be heated again to generate steam for recycling.

The invention provides a plasma gas conversion device, when the double electric field is a strong electric field, the plasma gas conversion device can be used for preparing aliphatic hydrocarbon and high-purity hydrocarbonOrganic compounds such as carbon ethers, higher alcohols and higher esters, and N₂、O₂、H₂SO₄、NH₃And the like.

The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method of plasma double electric field assisted gas phase reaction, comprising the steps of:

the reaction gas of the gas phase reaction is a gas comprising carbon monoxide and/or carbon dioxide;

introducing gas containing carbon monoxide and/or carbon dioxide into a reactor, wherein the reactor contains corona discharge double electric fields, the double electric fields comprise a first electric field and a second electric field, the first electric field is a high-voltage positive direct current corona discharge electric field or an alternating current corona discharge electric field, the second electric field is a high-voltage negative direct current corona discharge electric field, and the gas sequentially passes through the first electric field and the second electric field;

or the double electric field is a strong electric field, and the gas containing carbon monoxide and/or carbon dioxide is reformed into organic compounds containing aliphatic hydrocarbon, high-carbon ether, high-carbon alcohol and high-carbon ester under the action of the plasma double electric field;

the reactor is provided with a shell, and a reaction chamber is arranged in the reactor and is a metal cylindrical reaction chamber or a metal tubular reaction chamber; arranging a central electrode or a central metal rod in the center of the reaction chamber, arranging an opposite electrode or an opposite metal rod on the outer wall of the reaction chamber, optionally placing an insulating dielectric cylinder in the electric field, forming a dielectric barrier discharge gap to form a dielectric barrier discharge field, and generating a strong electric field in a corona discharge double electric field; or

A central electrode or a central metal rod is arranged in the center of the reaction chamber, a counter electrode or a counter metal rod is arranged at the far end of the reaction chamber in a ground mode, an insulating medium cylinder is not arranged in the electric field, and at the moment, a weak electric field is generated in the corona discharge double electric fields.

2. The method of claim 1, wherein the reaction gas is flue gas, water gas, syngas, and/or automobile exhaust.

3. The method according to claim 2, characterized in that the reaction gas is in particular: flue gas and water vapor, or water gas or synthesis gas optionally mixed with hydrogen.

4. The method according to claim 1, wherein different organic and inorganic compounds are prepared by adjusting the electric field intensity of the plasma double electric field, which is adjusted by the distance between the electric field center electrode and the opposite electrode, whether the insulating medium is added, and the dielectric constant thereof.

5. The method according to any one of claims 1 to 4, characterized in that at least one reaction chamber has an alternating corona discharge electric field or a positive corona discharge electric field and at least one other reaction chamber has a negative corona discharge electric field, an electrode or a metal rod is arranged in the center of the corona discharge electric field, and an alternating corona discharge electric field source or a positive corona discharge electric field source and a negative corona discharge electric field source supply power to the electrode or the metal rod; the electrodes or metal rods provide high energy electrons that can be adsorbed to the gas.

6. The method according to claim 1, wherein the number of the metal cylindrical reaction chambers or the metal tubular reaction chambers in each electric field section is one or more, and a plurality of the metal cylindrical reaction chambers or the metal tubular reaction chambers are configured to be arranged in parallel to form a cylindrical or tubular array group.

7. The method according to claim 1, wherein the reformed gas mixture is treated to obtain a gas-phase product and a liquid-phase product, and the treatment is performed by a gas-liquid separator or a distiller.

8. The method of claim 7, wherein the liquid phase product is further subjected to distillation to separate water by using an atmospheric distillation tower, and the water is further heated into steam to be circulated back to the reactor to continue to participate in reforming.

9. The method as claimed in claim 1, wherein a plurality of the double electric field reactors are connected in series, and the gas phase product of the former reactor is passed into the latter reactor to further convert the carbon source in the gas phase into an organic compound or an inorganic compound.